Lubricating composition



= points.

Patented Mar. 17, 1942 wnmca'rme COMPOSITION Carl F. Prutton, Cleveland Heights, Ohio, assignor, by mesne assignments, to The Lubri-Zol Development Corporation, Cleveland, Ohio, a cor poration of'Delaware No Drawing. Application December 21, 1938,

Serial No. 247,000

. 13 Claims. This invention relates, as indicated, to lubricants and more particularly to lubricating compositions and methods'of lubricating having certain advantages over such compositions and methods now familiar to those skilled in the art.

This application is a continuation in part of co-pending application Serial No. 737,070, filed July 26, 1934, and copending application'Serial -No. 755,987, 'filed December 4, 1934.

contact surfaces of cylinders and piston rings in internal combustion engines, and many other Such pressures tend to cause the rupture of the continuous thick film of lubricant which separates bearing surfaces under more moderate conditions. A region of thin film lubrication results which is also sometimes described as boundary lubrication.

. A particular object of my invention is; therefore, to provide a lubricant and method of lubricating which will function to advantage under conditions of extreme pressure and 'efiectively prevent seizure andscoring of the relatively moving metallic surfaces being lubricated.

Other objects of this invention will appear as the description proceeds.

- To the accomplishment of the foregoing and related ends, this invention, then, comprises the means hereinafter fully described and particularly pointedout in the claims. The following description sets forth in detail certain approved combinations of ingredients embodying my invention, such disclosedmeans constituting, however, but certain of the various formsin which the principleof the invention may be employed. Broadly stated, this invention contemplates the combined use in lubricating compositions of a soap (salt) or ester of a naphthenic acid and a separate halogenated organic compound.

When liquid compositions are desired, as, for instance, in the lubrication of Diesel engines, it

is obvious that only relatively small proportions of the soap should be added to the hydrocarbon base oil. Since, however, it has been found that the presence of even small amounts of the naphthenate will considerably enhance'the effectiveness of the separate halogen compound, liquid compositions are satisfactory formany purposes a id may contain as little as 0.1% of the soap or ester although from about 1% to about'5% by weight, based on' the amount of oil, is generally more desirable and where solid or semi-solid greases are to be employed much larger percentages of the soap may be suitable, up to. about The base oil employed in the composition of this invention is generally mineraloil but it is to beunderstood that any other suitable hydrocarbon lubricating oil, whether naturally occurring or synthetic, may be employed as the-oil base.

It is also within the contemplation of this invention to provide the addition agents in the form of a concentrate in a suitable oil, said oil containing rather high percentages of the addition agents. Such concentrates may be employed for future blending with a lubricating oil in the proportions desired for the particular conditions of use.

The following list of naphthenates suitable for use in accordance with the invention is intended to be illustrative only and it is to be understood that various other compounds coming within the group of salts (soaps) and esters of naphthenic acids broadly are included within the scope of the invention: A. Salts (soaps) of naphthenic acids p (1) salts of alkali metals, e. g.,

Sodium naphthenate Potassium naphthenate (2) Salts of alkaline earth metals, e. g.,

Barium naphthenate alcium naphthenate Strontiumnaphthenate Magnesium naphthenate (3) Salts of other metals such as,

Aluminum naphthenate Lead naphthenate Zinc naphthenate (4) Salts of organic bases, e. g.,

Aniline naphthenate Toluidene na hthenate Y Dimethyl anifine naphthenate Quinoline na hthenate Pyridine nap thenate B. Esters of naphthenic acids (1) Aliphatic esters, e. g.,

0 ethyl naphthenate Ethyl naphthenate Butyl naphthenate Amyl naphthenate Lauryl naphthenate (2) Aromatic esters e; g.,. Plienyl naph enate Benzyl naphthenate These naphthenates have the effect, when employed in lubricating compositions in conjunction with a separate organic halogen compound, of rendering the halogen more active so that the extreme pressure characteristics of the lubricant are considerably improved over those afforded by the same halogen compound when employed as pounds as notedmay be either:

the sole addition agent. This activation permits the use of halogenated organic compounds which would otherwise be too inactive for a particular purpose and also so enhances the effectiveness of various other organic halogen compounds that they may be employed to good advantage in cut-- The halogenated oxygen-free organic com- A. Aliphatic such as halogenated:

I Hydro carbons,

Notably, those containing from four to ten carbon atoms e. Chlorinated or fiuor nated hexane Chlorinated or fluorinated octane Chlorinated or fluorinated decane l i lsl d dt :1 n 1 r ary, secon ary an er ary e. g. exyamines, di-amylamines, tri-amyiamines such as: Chlorinated or iiuorinated tri-am l amine Chlorinated or fluorinated hexy amines Also Chlorinated or fluorinated tributyl amine III. Nitriies Halogenated ethyl nitrile Halogenated butyl nitrile or (preferable for certain types of uses as noted above) B. Cyclic compounds, such as halogenated:

I. Benzene and related compounds such as:

alogenated benzene, e. g.,

The dichlorbenzenes, notably the ortho compound Ortho-dibrom benzene The fluorinated benzenes (2) Halogenated derivatives of benzene such as (a) Halogenated homologs of henzene, e. 3., Mono-chlor toluene Mono-chlor xylene Mono-chlor cymene Ethyl mono-chlor benzenes Propyl mono-chlor benzenes Di-ethyl mono-chlor benzenes Ethyl dichlor benzenes Prop 1 dichlor benzenes Di-e yl dichlor benzenes Di-ethyl tetrachlor benzenes- (b) Halo enated amino derivatives of nzene, e. g. Chlorinated aniline Mono-chlor aniline (preferably the ortho-compound) Mono-chlor di-methyl aniline Chlorinated toluidines Chlorinated xylidines Chlorinated diphenylamme (c) Halogenated hydrobenzenes, e. g., Hydrogenated dichlor-benzenes such as dichlorhexahydrobenzene (dichlor cyclohexane) (3) Halogenated aromatic nitriles, e. g.,

' Ch orinated henyl nitrile II. Polyphenyls, and rela ed compounds, including diphenyl, diphenyl benzenes, etc., such as, (1) Chlorinated dighenyl, e. g.,

Mono-chlor iphenyls Di-chlor diPhenyls Tri-chlor d henyls (2) Brominated d phen l, e. g. The mono-brom i henyls (3) Fluorinated digheny (4) Hnlogenated eriva tives of diphenyl,

such vas, (a) Halogenated homologs of dienyl e. g., 7 Ch orinated meth l diphenyls Chlorinated ethyl ghenyls (b) Halogenated amino erivatives of diphenyl, e. g. Chlorinated amino-diphenyls Qhlorinated amino methyl diegiheny (c) Halogenat hydrodifihenyls, e.-g.,

Ch orinated pheny hexahdydrobenzene Chlorinated dodecahydrc iphenyl i I and 10 phenyls.

Some of the best examples of the aromatic compounds are:

III. Naphthalene, such as (1) Chlorinated naphthalene, e. g., a-mono-chlor na hihalene (2) Brominated naph alenes, e. g.,

a-monobrom na hthalene 3) Fluorinated naph a ene 4 Halogenated derivatives of naphthalene sue as: (a) Halogenated homologs of naphalenes,

Chlorinated methyl naphthalene notably the al ha compound, chlorinat gropyl,

isopropyl subs tuflon products of naphthalene (b) Halogenated amino derivatives of naphthalene, e. ti,

Chlorinated naph ylamines Mono-chlor a naphthyl amine (c) Halogenated hydronaphthalenes,

e. g. Chlorii'iated decahyd ronaphthalene 1V. Phenanthrene and anthracene and related compounds, such as: i (1) Chlorinated phenanthrene, chlorinated anthracene (2) Halogenatedderivatives of phenan threne and anthracene, such as: (a) Halo enated homologs Ch orinated l-met yl phenanthrene Chlorinated 3-methyl plienanthrene Chlorinated 9,10 dimethyl henanthrene Chorinated propyl and isopropyl derivatives of phenanthrene Chlorinated dimethyl anthracenes Chlorinated a-methyl anthracene Chlorinated B-methyl anthracene Chlorinated propyl and iso propyl derivatives of anthracene (b) Halogenated amino derivatives,

Chlorinated phenanthr-ylamines Chlorinated anthramines (c) Halogenated hydrophenanthrenes and halogenated hydroanthracenes, e. g

Chlorinated re tene oil (contains hydro retene) V, Chrysene, Sicene, and related compounds inc uding eir derivatives, such as homologs, amino derivatives and other substitution products.

VI. Bridged ring compounds, such as the terpenes and related compounds, and their derivatives, e. g., chlorinated pinene.

VII. Heterocyclic compounds, such as pyridine, quinoline, pyrrole, thio hene, and derivatives of them, e. g., mono-c lor pyridine.

Very satisfactory results may be obtained when two or more different halogens are present in the same molecule, orthobrom-chlor benzene, ethylbrom chlor benzenes, and the fluorinated chlorine Good examples of halogenated aliphatic hydrocarbons are:

Fluorinated ntane Fluorinated exane Fluorinated octane Fluorinated di-iso-butene l-Ialogenated petroleum derivatives, particularly halogenated petroleum oils and waxes. Halogenated oxygen bearing organic compounds Here, as above, com series with the halogen a unds of the aromatic,

ched to the ring are t acres favored for'purposes' in which it is' desirable to have the halogen presentin its most stable com-'- bined form. However, for certain uses the halogenated oxygen-bearing aliphatic compounds have been found to be more eflective and satisfactory.

The oxygen-bearing compounds may, for convenience, be classified as follows:

etc., also compounds of the bridged ring pe, such as the terpenes, and re ated compounds.

(b) or the class including the cycloparatfins, cyclo-olefines, etc. Examples of this class are oxygen-bearing derivatives of the following:

( 1) Hydrogenation products of benzene (e.

cyclohexane', cyclohexene,

cyclohexadiene Such as hydrogenated phen l,

notably: Cyclohexanol, i-' I tetra-hydroh dro-phenol,

p enol. (2) Hydrogenation products of na h thal'ene (e. g. decahy ronaphthalene, tetra-hydronaphthalene, etc.) Such as th hydrogenated thols.

such as naphacid, etc

t Of mixed type such as derivatives of indene, hydrinene, hydranthracene,

etc. B. "Heteroc clic type compounds (a) O the aromatic or allied type including derivatives of pyridine, quinoline,

e (b) Other types such as furfural, turan and its derivatives and derivatives of thiophene, pyrroie, etc.

The oxygen-bearing derivatives of the foregoing compounds may also be classified according to the nature of the attachment of the oxygen to the molecule, viz.:

I. Directly attached t'o one or more carbon atoms, as in the case of (1') Ethers and analogous compounds I (2) Compounds containing the --(i0H radicle,

such as alcohols and other derivatives of carbinol (including phenols, cresols, naphthols, e

(3) Compounds containing the carbonyl C=O radicle, such as amides, aldehydes, ketones, 0fflll1(3 8.0ldS, esters and salts of organic ac ds, thio-acids and esters of thio-acids (4') Compounds in which oxygen forms apart of the ring structure, e. g., furan and its derivatives, etc. (5') Compounds with inorganic radicle where the oxygen is directly attached to carbon atom: Arsenite Hypoch lorite Phosphite Thiophosphate Thiophosphite B-Hydroxylamines v II. Indirectly attached through the means of some other atom, i. e., in the form of an inorganic rudicle,

e. Arsenate phoxide Thio-sulphate The following table indicates some'of'the, compounds which are particularly suitable for use in accordance with the present invention:

A. Aromatice. oChlor enol Monoch or a-naphthols Alcohols, e. in The chlorenzyl alcohols Ketones, e. g.,

Mono-chlor benzophenones Chlor naphth l ketones Chlor-methylenzophenones Acids, e. E"

Chlorp enyl acetic acids Chlor salicylic acids Chlor phenyl stearic acids Esters e. g.,

Meth l chlorbenzoates Ethy chlorbenzoates Butyl chlorbenzoates Dlmeth l chlor hthaiates Di-ethy chlorp thalates Dibutyl chlorphthalates Methyl chlor salicylates Methyl chlor-phenyl-stearatcs Ethers, e. g.,

Chlorinated di henyl ether Chlo henyl e ylethers Chlor nated dixen v l ether Chlorinated dina thyl ether Alkylated chloriphenyl ethers ounds Ha ogenated cyclohexanol Halogenated esters of naphthemc acids 8) 0x gen-bearing heterocyclic compounds a.) Halogenated furane and derivatives of urane, e. g., Halogenated esters of pyromucic, acid (furoatesf). Halogjeifiated urfuryl alcohol and esters o e. g. Chlorinated furfur vl acetate (b) Halogenated oxygen-bearing derivatives of thiophene and pyrro e. g.,

Chlorinated esters of-thiopheue car boxylic acids and chlorinated esters of pyrrole carboxylic acids B. Chain compounds Alcohols Fluorinated octyl alcohol- Fluorinated decyl alcohol Fluorinated laur 1 alcohol Fluorinated cety alcohol M (2) Esters Methyl dichlorstearate Chlorinated tri-laur l hos hate Chlorinated tri-ethy p osp ate (3) Ketones Chlorinated dibutyl ketone Chlorinated di-amyl ketoue It is, of course; to be understood that the above lists of compounds are intended -merely to illustrate the type of compound suitable as one component of the addition agent of this invention and are not to be construed as limiting said component to the particular groups or examples there disclosed.

It is believed that under conditions of extreme pressure the halogenated addition-agents of this invention react chemically or physico-chenilcally with the metallic surfaces to form a non-fluxing vention is not intended to be limited, however, by any particular theory or explanation of the action upon the metallic surfaces.

All of the various halogens are effective when employed in accordance with the present invention but chlorine is generally preferred, inasmuch as it is the least expensive and one of the most effective of the halogens. Bromine and fluorine are more expensive and the latter is relatively difficult to handle but they are each usable in accordance with this invention. Iodine is not so readily obtainable as the other halogens and is quite expensive but" it also is satisfactory in providing eflective addition agents, It should also be noted that two or more difierent halogens may be present in the same molecule. .The bromchlor and fiuorinated chlorine or bromine compounds give especially satisfactory results. When used in conjunction with a naphthenate, an amount of from about 0.1% to about 20% by Non-aromatic oxygen-bearing organic ring comsurface which will not seize or score. This lnagent by volatilization will be less for compounds having a low volatility, the vapor pressure of the compounds should, for most purposes, be less than atmospheric pressure at temperatures up vapor pressure be less than atmospheric at temperatures up to 170 C. In the case of'compounds which are stable at temperatures up to their boiling points, this condition may be expressed by stating that the boiling point of the compound should, in general, be higher than combustion engines, higher than 170 C.

While mineral oil generally is the principal ingredient of the lubricant, it is not essential that it .be the only ingredient other than the addition i to 140 C. 'It is usually desirable, especially for use in internal combustion engines, that the,

,20 140 C., and for certain uses, such as in internal agent, provided that there be no additional ingredient which is incompatible with such addition agent. It is within the contemplation of this invention to include, if necessary or desir-. able', such other addition agents as are commonly added to improve the viscosity index or cold test of the lubricant and a lubricating composition according to this invention which also has a separate oiliness increasing agent has been found to be especially effective.

as regards the details described, provided the features stated in any'ofthe ,following claims, or the equivalent of such, be employed.

I therefore particularly. point out and distinctly claim as my,invention:

1. A lubricating composition comprising a hydrocarbon oil, from about '.l% to about 5% of a naphthenate, and a separate halogenated organic compound.-

2. A lubricating composition comprising a hydrocarbon oil, from about .1% to about 5% of a naphthenate, and a separate halogenated organic ring compound. 1

3. An extreme pressure crank-case lubricant for internal'combustion engines comprising a major proportion of a hydrocarbon oil, from about .1% to about 5% of a naphthenate, and a separate halogenated organic compound.

4. A lubricating composition having as a prin- Other modes of applying the principle of th invention may be employed, change being made hydrocarbon oil, from about 0.1% to about 5% of aluminum naphthenate, and from about 0.1%

cipal lubricating constituent, the combination of mineral lubricating oil, from about .1% to about 5% of an oil-soluble naphthenate, and a stable, oil-soluble, halogenated organic compound, said compound having a vapor pressure less than atmospheric at a temperature of 140 C. and

.present in an amount less than 10%, based on the amount of mineral oil, but sumcient to provide a lubricating composition effective to 'prevent seizure and scoring of relatively moving metallic surfaces under pressures substantially in excess of 10,000 pounds per square "inch.

5. An extreme pressure crank-case lubricant for intemal combustion engines comprising a major proportion of a hydrocarbon oil, from about .1% to about 5% of a naphthenate, and a separate chlorinated organic compound.

6. An extreme pressure crank-case lubricant for internal combustion engines comprising a major proportion of a hydrocarbon oil, from about .1% to about 5% of a naphthenate, and a separate chlorinated organic=ring compound.

7, A lubricating composition comprising a hydrocarbon oil, from about 0.1% to about 10% of a chlorinated organic compound, and from about 0.1% to about 5% of a salt of a napthenic acid.

8. A lubricating composition comprising a hydrocarbon oil, from about 0.1% to aboutl0% of a chlorinated aromatic compound, and from about 0.1% to about 5% of a salt of a naphthenic acid.

9. A lubricating composition comprisinga hydrocarbon oil, iromabout 0.1% to about 3% of a chlorinated aromatic compound, and from about 0.1% to. about 5% of a salt of a naphthenic acid.

10. A lubricating composition comprising a hydrocarbon oil, from about 0.1% to about 5% of aluminum naphthenate, and from about 0.1% to about 10% oi a separate halogenated organic compound.

11. A lubricatingcomposition comprising a to, about 3% of a separate chlorinated organic ring compound.

12. A lubricating composition comprising a hydrocarbon oil, from about 0.1% to about 5% of calcium naphthenate, and. from about 01% to about 10% of a compound.-

separate halogenated organic 13.,A lubricatingzcomposition comprising a hydrocarbon oil, from about 0.1% to about 5% of lead naphthenate, and from about 0.1% to about 10% of a separate halogenated organic compound. 7

CARL F. P'Ro'rroN. 

